Aldehyde reaction products with nitrogen-containing methylene compounds



,assigned to Patented Apr. 22, 1941 I 1 UNITED STATES PATENT OFFICE2,239,441 mama nmcrron rno uo'rs wrrn macaw-comma METHYLENE COMPOUNDSGaetano r. nmeu manna, Mass., assignor to General Electric Company, acorporation of New York No Drawing. Application June 20, 1940, SerialNo. 341,531

20 Claims. (01. 260-43) v organic compounds having a methylene groupattached to two adjacent carbon atoms, which are at least double-bondedand in turn are each attached to adjacent nitrogen atoms, constitute aclass of substances which on reaction with aliphatic aldehydes, e. g.,formaldehyde, form light- .colored, light-stable resinous products.

Exa'mples of such organic compounds are malonic diamide, methylenecyanide, cyanoacetamide,

etc. The grouping of this .class of substances may be representedgenerally as CEN I Cfig ll GEN C GEN v As will be noted from the abovegraphic formulas,

the carbon atoms adjacent to the methylene group are at leastdouble-bonded and may be attached either to a double-bonded element,

e. g., oxygen, sulfur, selenium, etc., or to a divalent radical, e. g.,an imine radical (=--NH) I am aware that the broad suggestion has beenmade heretofore that resinous compositions may be obtained by condensingformaldehyde or-its polymers with polyamides of polycarboxylic acids,more particularly those containing more than four carbon atoms, e. g.,polyamidesof adipic' acid, suberic acid, phthalic acid, etc. It also hasbeen suggested that the properties of such resinous condensationproducts may be altered by adding before, during or after thecondensation substances capable of reaction with formaldehyde, e. g.,urea and its derivatives, phenols and aniline. However, to the best ofmy knowledge and belief, resinous'compositions were not prepared priorto my invention by intercondensing an allphatic aldehyde and an organiccompound having the graphic formula where X is a member of the class"consisting of nitrile radicals, and amide and thioamide radi- -calshaving at least one hydrogen atom attached directly to the amidenitrogen, which compound is'designated generally as Likewise, to thebest of my knowledge, and belief, it was not known or hereafter forbrevity malonic compound.

appreciated prior to my invention that particularly useful, relativelyinexpensive resins could be obtained by inter-condensing ingredientscom- :prising an aliphatic aldehyde, a malonic compound, and a differentorganic compound capable of forming a methylol derivative as anintermediate during the resin formation, e. g., a phenol; or, byintercondensing a malonic compound (or a partial condensation product,e. g., a methylol derivative, of a malonic compound and an aliphaticaldehyde, e. g., formaldehyde) with a partial condensation product, e.g., a

'methylol derivative, of a phenol or a urea (or other methylol-formingorganic compound) and an aliphatic aldehyde.

The class of methylene-containing compounds 7 under consideration havebeen. foundto react with aliphatic aldehydes, e. g., formaldehyde, inthe presence of either alkaline or acid catalysts, or without thepresence of a catalyst, to form colorless resins varying from vitreousand semivitreous products to fine powders all of which form plasticmasses under heat, or under heat and pressure, and can be molded. In thecured state the resins are resistant to sunlight. They may be produced,therefore, in light colors including the pastel shades.

Any substance or catalyst which has an acid or an alkaline nature may beused to obtain the acid, alkaline or neutral condition under which thereactants are intercondensed. For example,

I may use ammonia, calcium hydroxide, sodium and potassium hydroxides,carbonates and bidiamine, triethylene tetramine aniline, pyridine,

morpholine, biguanidine, glycine, sodium glycinate, sodium acetate,etc.; also, inorganic and organic acids such as hydrochloric, sulfuric,phosphoric, acetic, acrylic, crotonic, malonic, etc., acid salts such assodium acid sulfate, secondary ammonium phosphate, mono-sodiumphosphate,

mono-sodium phthalate, etc.

' In producing the new condensation products of this invention, thereaction between the comtion between the components may be initiated ata pH above 7.0-and completed at a pH below 7.0. The dehydration of theresin may be carried out at atmospheric pressures with the applicationof heat, e. g., at 50 to 100 C., or at lower temp ratures by usingvacuum.

The condensation reaction preferably is carried out in the presence ofan alkaline catalyst, inasmuch as immediate reaction then takes placebetween the reactancts. With an acid catalyst the time of reaction ofthe aliphatic aldehyde :ith the malonic compound is-longer. n heattreatment the alkaline-catalyzed condensation products advance insoftening point to a stage where they are not readily fusible, but arenot in the cured state at. this point. Usually the addition of an acidmaterial such, for example, as acid potassium sulfate, acetic acid oreven an acidic synthetic resin suchas an acidic alkyd resin, or anacidic gum such as shellac, produces a thermosetting resin that may becured to an insoluble, infusible state.

The products may be obtained with glass clarity if a light-coloredacidis used in the cure. Fillers,

dyes, pigments, etc., may be incorporated into the resinous mass and maybe mixed with the resin either in the syrupy stage or in the dehydratedstate. The alkaline syrup may be converted to the acid side andmloldable sheets prepared by impregnating with it paper, cloth or otherfibrous 7 material. Translucent or opaque laminated ma- I terials thusmay be made.

Because of the peculiar structure of the malonic compounds with whichthis invention is concerned, it is possible to utilize them in theconversion of fusible phenolic resins to the infusible state. It is tobe observed that condensation products of such compounds and analiphatic aldehyde have an ethylenic structure. Thus, when formaldehydeand malonic diamide are condensed, the following reaction occurs:

0 dNH:

conncmon c +scmo om==o +n,o

coma conncmon The product of the reaction is in itself not only aldehydeand at least one organic compound having the graphic structure where Xis a member of the class consisting of nitrile (-C N) radicals, andamide and thioamide radlicals having at least one hydrogen atom attacheddirectly to the amide nitrogen. Illustrative of such amide and thioamideradicals are those which may be represented by the formulas -c ON\ and/H -CSN I where R represents hydrogen, or alkyl, aryl, aralbe employedas desired or as conditions may require, but the proportions usually arewithin the malonic compound).

range of to 6 or 7 mols aliphatic aldehyde for each mol of the maloniccompound. Preferably I use approximately 1 to 4 mols aliphatic aldehydeper mol of the malonic compound. The resulting methylol or methylenederivatives then may be condensed with another methylol-forming organiccompound, e. g., a urea, a phenol, etc.,

or with a partial condensation product, e. g., a methylol derivative, ofa phenol (or other. methylol-forming organic compound) and an aliphaticaldehyde. In preparing such partial condensation products of, say, aphenol and an aliphatic aldehyde, the mol ratios of reactants may bevaried as desired or as conditions may require. but usually theproportions are within the range of to 6 or '7 mols of the aliphaticaldehyde for each mol-of the phenolic body, for example from, -1 to 4mols of the former for each mol of the latter.

The ratio of the total molar amount of phenolic body (or othermethylol-forming organic compound) and malonic compound to aliphaticaldehyde may vary considerably, depending upon the particular startingreactants, the conditions of reaction and the particular propertiesdesired in the end-product, but generally is within the range of to 6 or'l'mols aliphatic aldehyde for each mol total phenolic body andmaloniccompound (that is, 1% to T2 or l4-mols aliphatic aldehyde for each twoniols of total: phenolic body and each mol of total phenol and malonic ound. Mainly for economic reasons I prefer exceeding substantially onemol of the malonic phatic aldehyde, specifically formaldfide, for

compound for each mol of phenol (or equivalent material); and usuallyemploy less than 0.8 mol, more particularly from about 0.05 to 0.7 molof the former for each mol of the latter.

In producing the condensation product'swherein at leastthree reactantsare employed, I may Particularly good results are obtained with the useof 1% to 2% mols all- .use notintercondense the components under variousconditions. For example, all the components may be mixed together andthe reaction caused to proceed under acid, alkaline or neutralconditions. Or, I may eifect partial condensation between an aliphaticaldehyde and a phenol (orother methylol-forming organic compound), thenadd the malonic compound and effect further condensa tion. Or, I mayfirst partially condense the malonic compound with an aliphatic aldehydeunder acid, alkaline or neutral conditions and then add, Say. a'phenoland effect further condensation. Or, I may separately pa'rtiallycondense (l) a phenol and! an aliphatic aldehyde and (2) a maloniccompound and an aliphatic aldehyde, thereafter mixing the two productsof partial condensation and effecting further condensation therebetween.The reactants of (1) and of (2) initially may be condensed under acid,alkaline or neutral conditions. The above reactions may be carried outin the presence or absence of other substances as, for example, fillers,solvents or diluents, other natural and synthetic bodies, etc.

Depending upon the particular reactants employed and the particularconditions of reaction, the intermediate (potentially reactive)condensation products vary from clear, water-soluble liquids to milkydispersions. These liquidintermediate condensation products may beconcentrated or diluted further by the removal or the addition ofsolvents to form liquid coating compositions of adjustedviscosity andconcentration. These liquid compositions may be used, for instance, assurface coating materials, in produc- 35 ing laminated articles, etc.The liquid intermediate 'products may be used alone, or mixed withfillers, dyes, pigments, lubricants, etc.,

.in the production of molding compositions. Also,

these products may be dried and granulated to form clear, unfilled,heat-convertible resins.

In order that those skilled in the art better may understand how thepresent invention may be carried into effect, the following examples aregiven by way of illustration. All parts are by weight.

Example 1 Malonic diamide parts 25 Aqueous solution of formaldehyde(approximately 37.1% HCHO) parts 79.3 Sodiumhydroxide in parts water(calculated on the weight of malonic (11- amide used) per cent 0.25 a

The above components are mixed at room temperature and allowed to standundisturbed for from l to 24 hours. The'solution is then evaporated bythe application of heat, at atmospheric or sub-atmospheric pressure, oris evaporated with the aid of vacuumalone.

The reaction may be carried out athigher temperature either by firstbringing the malonic diamide and formaldehyde to reflux temperature andthen slowly adding the catalyst, or by first mixing all of theingredients'and then raising the temperature. I

The final resin is the same, regardless of the amount of formaldehydeused, provided at least 3 mols formaldehyde are present. That is,theproduct is-tri-methylol malonic diamide, viz.:

' connomon Room-on ooNncrnoH which probably dehydrates through differentstages to tri-methylene malonic diamide by the loss of 3 mols of water:

OON=CH1 5 om=c 00N='cm The resinous product obtained as above outlinedmay be used to convert a fusible phenolic resin to the infusible state,yielding light-colored resinous products. Thus: A phenolic resin isprepared from redistilled phenol, formaldehyde and a sulfuric acidcatalyst. After reaction has taken place between the ingredients for onehour, the water'layer is decanted and the resin washed with water toremove as far as practical all traces of the acid. The product then isdehydrated under vacuum (27' mercury) at about 100 C. until it isbrittle. A very light-colored, novolak-type resin results. The followingtable shows the results of the preparation of several resinous productsfrom the novolak-type resin prepared as outlined above, using, a malonicdiamide-formaldehyde reaction product prepared as also outlined above.The preparation of the-following resinous products was effected byprocessing equal parts by weight of the malonic diamide-formaldehydereaction product and the washed phenolic resin. The temperature of themalonic diamide-formal 30 dehyde condensation reaction is given in eachcase, as is also the color 0f the product obtained when equal parts ofthe malonic diamide-formaldehyde reaction product and 'phenolic resinare molded at 150 C'. for 5 to 10 minutes.

ii't fi t a re 10.

Temp. oi Reaction product figfg g reaction with phenolic resin diamide)'to (EH50 40 4 1:7 00 Rcddish pink, clear. 3 1:7 90 Do. I 2 1:7 90 Lightpink, clear. 1 1:7 90 D0. ed 1:7 90 No real euro. 4 1:7 Reddish ink,clear. 1 1:7 50 Light ye low pink,

0 ill. 4 l :4 50 Light ycllow,opaquo. 1 1:4 50 Light cream, opaque- 41:4 90 Slight pink cast,

clear. 1 1:4 90 Light ivory, opaque. 1 1:3.2 50 ivory. 4 1:3. 2 50Yellow, opaque. l 1 :4 Room temp. Ivory, opaque. 1 1:4 90 Do.

'N0'r1t. The percentages of NaOH are in addition to the amount requiredto neutralize the formaldehyde solution.

Example 2 Parts Malonic i i 25 Aqueous solution of formaldehyde(approximately 37% HCHO 139 are heated under reflux-at boilingtemperature for 12 hours with no added catalyst and then dehydratedunder vacuum to a water-white, glassy resin that is soluble in water.This resin can' be cured to the infusible state. The addition of acidhastens the cure.

Example 3 Parts Malonic diamide 25 Aqueous solution of formaldehyde(approximately 37% HCHO) 139 Hydrochloric acid m5 parts water 1 arerefluxed 20 hours and dehydrated to a glassy,

water-whiteresin. This resin is soluble in water and can be cured to theinfusible state without further addition of acid.

Example 4 This example illustrates the preparation of a resin whereinone of the reactants is cyanoacetamide,

can

coNm

Parts Cyanoacetamide 15 Aqueous solution of formaldehyde (approximately37.1% HCHO) -1 48 Sodium hydroxide in 10 parts water 0.2

are mixed in the cold at about 30 0., the temperature rising to about 70C. An orange-colored solution results. After standing one hour theproduct is evaporated in an oven at about 70 C. for 10 to 15 hours. Theresin may be cured, and in the cured state is insoluble in water, whilein the uncured state it is partly dissolved with difll culty in boilingwater.

Example 5 This example illustrates the preparation of a resin whereinone oi. the reactants is N. N'-diphenyl malonic diamide,

(f H: JHIZH OH:

c-N n 8 Calls Parts N, N'-diphenyl malonic diamide Aqueous solution offormaldehyde (approximately 37.1% HCHO) -7 Sodium hydroxide in 20 partswater 0.1

are refluxed for '75 minutes. A creamy white, insoluble resinprecipitates out and is filtered ofl. from the water layer. The resin isdried at 70 C. It is insoluble in water and can be cured to aninfusible, insoluble state. The addition of acid hastens the time! cure.

Example 6 This example illustrates the preparation of a resin whereinone of the reactants is methylene are mixed at room temperature. Thereaction starts immediately and the temperature rises to 70 C. Thesolution is dehydrated, for example by heating for hoursin a 70 C. oven.The resin isamber-colored and in the uncured state is diflicultlysoluble in hot water. The cured resin is insoluble and infusible.

Example 7 This example illustrates the preparation of a resin whereinone of the reactants is N, N"-dibutyl malonic diamide',

comrclm comical.

7 Parts N, N'-dibutyl malonic diamide 21.4 Aqueous solution offormaldehyde (approximately 37.1% HCHO) 243 Sodium hydroxide in a smallamountot water 0.21

are mixed and heated at boiling temperature under reflux for 1 hour. Thereaction mass separates into two phases on standing. The entire mass isdehydrated by heating it in an open vessel on a 0. hot plate. A soft,sticky, colorless, thermoplastic resin results.

Example 8 This example illustrates the preparation of a resin whereinone of the reactants is N, N'-dicyclohexyl malonic diamide,

C ONE-C CHI-CHI Parts N, N'-dicyclohexyl malonic diamide 13.3 Aqueoussolution of formaldehyde (approximately 37.1% 116110) 12.2 Sodiumhydroxide in a small amount of water 0.13

are mixed and heated at boiling temperature under reflux for 1 hour. Thereaction mass separates into two phases on standing. The entire mass isdehydrated by heating it in anopen vessel on a 150 C. hotv plate. Thedehydrated prodnot is a soft, sticky, colorless, thermoplastic resinsomewhat wax-like in character.

Example 9 This example illustrates the preparation of a resin whereinone of the reactants is N, N'-

diethanol malonic diamide, oomwlrnon c comiclmon Parts N. N'- diethanoimalonic diamide 19.0

Aqueous solution of formaldehyde (approximately'3'i.1% ECHO) 24.3 Sodiumhydroxide in a small amount of 7 water 0.19 are mixed and heated underreflux for 1 hour, yielding a homogeneous mass. Afterdehydratinginanopenvesselona150 C.hotplate,a soft, sticky, colorlessthermoplastic resin is obtained.

Example 10 This example illustrates how theamides 'used in Examples 7, 8and 0 may be intercondensed with a partial condensation product ofphenol and formaldehyde and the resulting resin used in making moldingcompositions and moldedarticles.

A master batch of a phenol-formaldehyde resin Anhydrous potassiumcarbonate .This yields a yellow syrup. Portions of. this 2 hours more at100 a hard, yellow resin.

, Parts Redistilled synthetic phenol 180 Aqueous solution offormaldehyde (approximately 37.1% HCHO) 390 in a small amount ofwater.-. 5.7

syrup (143 parts) are heated under reflux for minutes with4.5 parts eachof the amides used in Examples 7, 8 and 9. Each of the resulting liquidresins is neutralized with 1.21 parts oxalic acid, yielding a whiteheterogeneous mass. This mass is mixed with 57 parts alpha flock havingincorporated therewith 0.57 part zinc stearate. The resulting moldingcompositions are dried at 60 C. and then sheeted for approximately fiveminutes on diflerential rolls, one of which is hot H and the other cold.The sheeted compounds are ground. Molded articles are made from each ofthe ground compounds by molding for 5 minutes under a pressure of 2000pounds per square inch at about 150 C. The molded articles are well 2cured throughout and of light color.'

Example 11 Parts Malonic diamide 102 Acetaldehyde 132 Sodium hydroxidein 200 parts water 3 for an additional minutes at 100 C.

Example 12 Parts Malonic diamidn Acrolein 1 Sodium hydroxide in 100parts water The above components are heated under reflux for 2 hours,yielding a resinous mass when cold. This mass is dehydrated by heatingin an oven for about 17 hours at 55 0., then for about C. The resultingproduct is Almost allof the alkaline-catalyzed condensation products ofa malonic compound of the kind with which this invention is concernedand an aliphatic aldehyde, e. g., formaldehyde, exhibit hardening ordrying tendencies, but. are actually cured by the addition of substancesof an acid nature, e. g., organic acids, such as acetic, oxalic, citric,phthalic anhydride, salicylic acid and the like, or acidic salts such assodium acid phosphate, copper sulfate or the like, or acidic resins,such as shellac or acidic synithetic resins, e. g., acidic alkyd+typeresins. Resinous products prepared with the aid of acid catalystsusually cure without the necessity of any added substances.

The] finally cured resins are light-stable and unaffected by mostsolvents. With fillers, such as wood flour and alpha flock and theapplication of heat and pressure the resin may be mixed with thedehydrated resin or with the repart of citric acid hydrate is added.Paper action product in the syrupystage.

As further illustrative oi the scope of my invention, the followingexamples are given of the production of varnishes and laminated productsfrom phenol- -aldehyde resins in which the condensation productsdescribed herein are used as catalysts and co-condensing orco-polymerizing agents.

Example 13 1 Parts Malonic diamide-formaldehyde partial condensationproduct 5 Re-distilled, water-white phenol Aqueous formaldehyde solution(approximately 37.1% H0110)--- s 125 Sodium hydroxide in 5 parts water0.3

The malonic diamide-formaldehyde condensation product, sodium hydroxidesolution :and formaldehyde solution are mixed together and then thephenol is added immediately. The mass is refluxed for one hour anddehydrated to an internal resin temperature of 110 C. under 27" mercuryvacuum, after which an equal volume of alcohol is added. Paper sheetsare impregnated with the resin syrup to a 50% resin content, thereafterbeing dried in an oven at C.

for 35 minutes. The coated and impregnated laminated products are moldedat 135 C. for 1 minutes under a pressure of 2000 pounds per square inch.The molded product is cooled for 5 minutes before removing from themold. The molded product is a cured, translucent, almost pure white,laminated product.

Example 14 Same. formula as in Example 13. The reactants are heatedunder reflux for minutes. Fifty-eight parts water are removed and 0.53

sheets are dipped in the varnish, dried and molded under a pressure of1600 pounds per square inch at 140 C. for 15 minutes. The varnish inthis case is water-white and the molded product also is white.

Example 15 Sameformula as in Example 13. The malonicdiamide-formaldehyde -condensation product,

1 formaldehyde solution and sodium hydroxide somolded into rigid pieces.The filler may be 7 lution aremixed and allowed to stand for' one hourgThe phenol is then added and the mass is refluxed for two hours, partswater being removed- To the resulting mass is added 0.53 part citricacid hydrate, after which-sheets of paper are dipped in the liquidresin. The coated and impregnated sheets are dried at 100 C. for 90minutes. The laminated sheets are molded at C. for 30 minutes, using apressure of 1600 pounds per square .inch.

The malonic diamide-formaldehyde condensation product, formaldehydesolution and sodium hydroxide solution are mixed and allowed to mass isadded 0.26 part citric acid hydrate, afterwhich the liquid resinsdehydrated until most of the water has been removed. Thirty-five partsResin A:

ethyl alcoholare added. The resulting varnish is water-white. Sheets maybe dipped in this varnish, dried, and thereafter superposed and moldedas,in the previous examples.

It is to be observed that very light-colored varnishes having good curesand which do not discolor perceptibly at higher temperatures areobtained. The products are much lighter in color than those obtainedwith ordinary alkaline catalysts.

It is found that the varnish is much more stable if the alkali added tothe reaction mass is neutralized by the addition of at least thecalculated amount of acid. Any substances of an acid nature aresatisfactory, e. g., organic acids such as lactic, oxalic, acetic andthe like may be used. The varnishes remain water-white. Either a shorterreflux time may be used when the components are reacted in a watermedium or a longer reflux time may be used with an alcohol medium.

A characteristic of the products is that no sticking of the impregnatedsheets is encountered in the mold. Moreover, prolonged exposure tosunlight, for example up to a period of nineteen days, producedpractically no change in the color of the laminated sheets. Also, whenthe laminated products were immersed for 170 hours in water at roomtemperature while exposed to light, they showed no signs ofdelamination.

- satisfactorily. The condensation product cures the phenolic resin to avery light color and the final product has better light resistance thanphenolic resins cured in the ordinary manner with conversion agents suchas hexamethylene tetramme- As specific illustrations, the followingexamples are cited:

Example 17 Malonic diamide 150 Aqueous formaldehyde solution(approximately 37.1% I-ICHO) 475.6

Sodiumhydroxlde in parts water.--"

The malonic diamide and formaldehyde solution are mixed and made neutralto litmus, after which the sodium' hydroxide solution is added.

The resulting mixture is heated under reflux for one hour. filtered, anddehydrated under 27" mercury vacuum to an internal resin temperature of100 C., that is, until the resin no longer is tacky when cold. Theresulting resin may be processed, for example by milling with aphenolyde resin in any manner well known in the '75 a Parts art, or byusing a specially prepared phenolic.

resin such as those illustrated below:

Parts Phenol--- Aqueous formaldehyde solution (approximately 37.1% HCHO)260 Concentrated sulfuric acid in 60 parts water l 8 Resin B: PartsPhenol 300 Aqueous formaldehyde solution (approximately 37.1% HCHO)Concentrated sulfuric acid in 60 parts water are refluxed for one hour.The resin is washed until neutral and then dehydrated for 7 hours to aninternal resintemperature of C. under 27" mercury vacuum.

Resin C:

Same formula as for Resin B with the exception that 5 parts calciumcarbonate are added with stirring at the endo! the one hour refluxperiod, and the resulting resin is dehydrated to w an internal resintemperature'of 110 C. under 27" mercury vacuum over a period of 7 hours.

Example 18 a A molding resin may be prepared by mixing at -150 C. 35 to50 parts of the malonic diamide-formaldehyde res n of Example 17 with 50to 65 parts of one or another of the phenolic resins identified underExample 17 as Resins A, B and C. The color of the molded product islight ivory if the resin is molded by itself. Fillers, such as woodflour, alpha cellulose and the like, lubricants, dyes, pigments, etc.,may be incorporated with the resins to give thermosetting compositionsof good water-resistance.

Example-19 Parts Malonic diamlde formaldehyde resin of Example 17 Alphaflock Zinc stearate Lithopone The whole may be ball milled. sheeted onrolls or processed in a Banbury mixer, ground and molded to a whiteproduct.

The above components are mixed and processed in Example 19, yielding aStable, blue product.

Example 21 P Malonic diamide-formaldehyde partial condensation productAqueous formaldehyde solution (approx.

37.1% HCHO) 125 Sodium hydroxide in parts water 0.3 Phe'nnl 50 Themalonic diamide-formaldehyde condensation To the resulting liquid partsalpha flock. The

produce casting,resins and light-colored cast.

products. Generally 'the procedure for preparing the resins is the sameas described above, the compositions being dehydrated under vacuum andcast in the usual way.

It will be understood, of course, by those skilled in the art that myinvention is not limited to the specific, reactants named in the aboveillustrative examples. Thus, instead of formaldehyde other is heatedunder reflux production of laminated compounds engendering formaldehydemay be employed, for example paraformaldehyde, hexamethylene tetramine,etc. Other aliphatic aldehydes also may be used, the particular aldehydedepending upon economic considerations and the particular propertiesdesired'in the end-product.

For instance, in certain cases I may use propionaldehyde, butyraldehyde,methacrolein, crotonaldehyde, furfurai, etc., mixtures thereof, or mix-.tures of formaldehyde or compounds "engendering formaldehyde with suchaliphatic aldehydes.

Likewise, substances other than phenol itself may comprise themethylol-forming organic compound. For instance I may use other reactivephenolic bodies such as ortho, meta and para cresols, ortho, meta andpara chlorphenol, meta nitrophenol, p,p'-dihydroxy diphenyl propane,catechol, resorcinol, the xylenols, meta ethyl phenol, para tertiarybutyl phenol, para tertiary amyl phenol, the ortho, meta and para phenylphenols, the ortho, meta and para benzyl phenols, phenyl phenol ethane,etc., or mixtures of such aldehyde-reactable phenolic bodies.

The' new, intercondensation products 'of this invention in which thephenol is an orthoor para-substituted phenol containing three or morecarbon atoms in the substituent grouping are soluble in oils, as forexample drying and semidrying' oils, and insuch form, with or withoutfurther heat treatment of the oily solution of the resinous condensationproduct, may be used in the production of coating compositions such asvarnishes, enamels, lacquers, etc. Examples of substituted phenolsyielding oil-soluble intercondensation products are the 'orthoandparasubstituted butyl phenols, amyl phenols, coumar phenols, phenylphenols, z -ethyl hexyl phenols, terpene phenols, symmetrical phenylphenol alkanes, the nuclearly phenylatedphenyl, phenol alkanes, etc.;or, in general, an orth0- Ora P rato. include within its substitutedphenol having two reactive positions in the aromatic nucleus andcontaining at least three carbon atoms in the 'substituent grouping. Theterm a phenol" as used generally herein and in the appended claimstherefore is intended meaning not only-phenol (CsHzOH) itself but alsohomologues and derivatives of phenol. Y

Likewise malonic compounds other than malonic diamide may be usedseparately, or mixed with eachother or with malonic diamide. Illustrative examples of other malonicoompounds which may be employed aremethylene cyanide and compounds having the graphic formula Y R where Yrepresents a member of the class consisting of oxygen and sulfur and Rrepresents a member of the class consisting of hydrogen; alkyl, aryl,aralkyl, alkaryl, acyl, naphthyl, hydrocyclic and heterocyclic radicals;and nitro, halogeno, aceto, carbalkoxy and acetoxy derivatives of suchradicals. Illustrative examples of other malonic compounds which may beemployed are compounds having the graphic formula I GEN i R where Y andR have the meanings given'ln the preceding sentence. More specificexamples of compounds coming within the scope of the above formulas arecyanoacetamide monothio malonic diamide, dithio malonic diamide,cyanothio acetamide, N,N'-dialkyl (e. g., -dimethyl, -diethyl.-dipropyl, etc.) malonic diamides and dithioamides, N,N-diphenyl,-ditoly1, -dibenzyl, -diphenethyl, -d=icinnamyl, -di(para-hydroxy phen-5g) and -di(para-amino phenyl) malonic diamides and dithioamides; andN-methyl, -ethyl, -propyl, -isobutyl, -phenyl, -tolyl, -benzyl,phenethyl, -cinnamyl, -para-hydroxy phenyl, -paraamino phenyl, -acetoxy,and -carbalkoxy cyanoacetamides and cyanothioacetamides.

It also will be understood not only that mix- 'ple, as methylol-formingreactants I may use in certain cases mixtures of different phenols,mixtures of urea and urea derivatives (or substances of the nature ofurea) or tives and substances of the nature of urea, e. g., mixtures ofurea and thiourea, thiourea and allyl' urea, urea and melamine, thioureaand guanidine, etc., mixtures of a phenol and a urea or a ureaderivative (or a substance of the nature of urea), mixtures of amines,mixtures of an amine and a phenol, mixtures of an amine and a urea,etc.. The plurality of methylolforming bodies maybe intercondensed witha single aliphatic aldehyde or with a plurality of aliphatic aldehydes,using either a single malbnic compound or a plurality of malon'iccompounds.

Also, of course, a single methyiol-forming body -propionoxy, -butyroxymixtures of urea deriva- 3 may be intercondensed with one or moreallphatic aldehydes and one or more malonic compounds.

Additional examples of urea derivatives and substances of the nature ofurea which may constitute the methylol-forming compound used as amodifying reactant are given in my aforementioned copending applicationSerial No. 330,555. Other examples of methylol-forming bodies that maybe used alone or mixed with one another or mixed with a urea, a phenolor other methylol-forming compound are monohydric alcohols such asethyl; propyl, isopropyl, butyl, amyl, etc., alcohols; polyhydricalcohols, e. g.. ethylene glycol, diethylene glycol, glycerol,pentaerythritol, trimethylol nitromethane, etc; monoamides such asformamide,acetamide,stearamide, acrylic acid amides (acryloamides),benzamide, toluene sulfon'amide, etc.; polyamides such as adipicdiamide, phthalamide and the like; amines such as ethylene diamine,aniline, phenylene diamine, amino phenols, etc.

'If desired, the fundamental resinous condensation products of thisinvention may be modified by introducing other bodies before, during orafter condensation between the primary components. These addition agentsmay take the form of high molecular weight bodies with or withoutresinous characteristics, for example partially hydrolyzed woodproducts, lignin, proteins, protein-aldehyde condensation products,modifled or unmodified, saturated or unsaturated polybasicacid-polyhydric alcohol condensation products, sulfonamide-aldehyderesins, watersoluble cellulose derivatives, natural gums and resins'suchas copal, shellac, rosin, etc.; polyvinyl compounds such as polyvinylalcohol, polyvinyl acetate, polyvinyl acetals, specifically polyvinylformal, synthetic linear condensation products such as thesuperpolyamides, etc.

When compositions of increased plastic flow are desired, substances of aplasticizing nature may be incorporated into the synthetic bodies "ofthis invention before, during or after con densation between thereactants.

Examples of suitable plasticizers which may be used when necessary arethe phthalate esters, 'for instance 'dimethyl phthalate, diethylphthalate, dibutyl phthalate, etc., the phosphate esters such astricresyl phosphate, triphenyl phosphate, etc.

Dyes, pigments and opacifiers (e. 8., barium sulfate,zinc'-sulfide,titanium compounds such as the oxides, flaked aluminum,copper and the like) may be incorporated into the compositions to alterthe visual appearance and the form, sheets or cuttings of paper, cloth,canvas, etc., asbestos in powdered or long or short fiber length,Powdered or flaked mica, woodchips,

short or long wood fibers, synthetic or natural continuous threadedfibers, glass fibers in continuous filament or fabric (woven or felted!iomaetc.

In preparing molding compositions from the resinous bodies of thisinvention, the non-dehydrated or the partially dehydrated resins may becompounded with the above addition agents in accordance with procedureswell-known to those skilled in the art. The molding compositions may bemolded or extruded at elevated temperatures, e. g., between 100 and 170C., usually between 120 and 150 C., and at suitable pressures. Themolding pressures generally range between about 1000 and about 10,000 or20,000 pounds per square inch, more particularly from about 2000 toabout 4000 or 5000 pounds per square inch in the case of compressionmolding.

In addition to their use in molding compositions, the condensationproducts of this invention are especially suitable for use as fireretardants, water repellents and sizings when applied to wood or thelike, or to fibrous materials such as silk, cotton, wool, syntheticorganic fibers, etc., in continuous filament, thread, fabric or otherform. It will be understood, of course, that optimum resistance towater, fire, solvents, etc., is obtained only when the applied coatingor sizing is converted to the insoluble and infusible (cured) state.

. The modified or unmodified products of this invention have a widevariety of other uses, for instance in making interior finishingmaterials V for homes, oiiices, etc., in making buttons, clock cases,radio cabinets, dishes and other household utensils, decorativenovelties and various other -cast, molded and laminated articles ofmanufacture. They also may be used in making paints, varnishes,lacquers, enamels and other protective surfacing materials, in themanufacture of arc-extinguishing tubes capable of evolving an 1arc-extinguishing gas under the heat of the arc,

in the production of wire or baking enamels, for general adhesiveapplications, for instance in bonding or cementing together mica flakesto form a laminated mica article, as impregnants for electrical coilsand other electrical devices, and for other purposes.

Compositions comprising a condensation product wherein a ureaconstitutes an essential reactant in addition to an aldehyde and theabove described methylene compound are disclosed and claimed in mycopending application Serial No. 330,555. In my copending applicationSerial No. 169,465 I disclosed and specifically claimed compositionscomprising the product of reaction of a mixture comprising (that is, ofingredients comprising) an aliphatic aldehyde and malonic diamide.

What Iclaim as new and desire to secure by Letters Patent of the UnitedStates is:

1. A composition comprising a condensation product of a mixturecomprising an aliphatic aldehyde and at least one organic compoundhaving the graphic structure x CH:

where X is a member of the class consisting of nitrile radicals, andamide and thioamide radicals having at least one hydrogen atom attacheddirectly to the amide nitrogen.

2. A composition as in claim 1 wherein the allphatic aldehyde reactantis formaldehyde.

3. A resinous composition comprising the product of reaction of amixture comprising an an.

where X is a nitrile radical.

4. A resinous composition comprising the prodnot of reaction of amixture comprising an aliphatic aldehyde and at least? one organiccompound having the graphic structure where X is an amide radical havingat least one hydrogen atom attached directly to the amide nitrogen.

5. A resinous composition comprising the prod uct of reaction of amixture comprising an aliphatic aldehyde and. at least one organiccompound having the graphic structure X Cg:

where X is a member of the class consisting of nitrile radicals, andamide and thioamide radicals having at least one hydrogen atom attacheddirectly to the amide nitrogen.

7. A composition comprising an alcohol-modified resinous condensationproduct of a mixture comprising an aliphatic aldehyde and at least oneorganic ture where X is a member of the class consisting of nitrileradicals, and amide and thioamide radicals having at least one hydrogenatom attached directly to the amide nitrogen.

'8. A composition comprising a condensation product of a mixturecomprising an aliphatic alcompound having the graphic strucdehyde, aphenol and an organic compoundhaving the graphic structure where X is amember of the class consisting of nitrile radicals, and amide andthioamide radidehyde, a phenol and an organic compound having thegraphic, structure where X is a member or the class consisting ofnitrile radicals. and amide and thioamide radicals having at least onehydrogen atom attached directly to the amide nitrogen.

9. A- resinous composition comprising the product oi-reactlon of amixture. comprising formal- 'directly to the amide cals having at leastone hydrogen atom attached directly to the amide nitrogen.

10. An oil-soluble resinous composition comprising the product ofreaction of a mixture comprising (1) an aliphatic aldehyde, (2) anorthosubstituted phenol having at leasttwo reactive positions in thearomatic nucleus and containing at least three carbon atoms in thesubstituent grouping and (3) at least one organic compound having thegraphic structure x where X is a member of the class consisting ofnitrile radicals, and amide and thioamide radicals having at leastone'hydrogen atom attached directly to the amide nitrogen.

- 11. An oil-soluble resinous composition comprising the product ofreaction of a mixture comprising (1) an aliphatic aldehyde, (2) aparasubstituted phenol having at least two reactive positions in thearomatic nucleus and containing at least three carbon atoms in thesubstituent grouping and (3) at least one organic compound having thegraphic structure 1 X a where X is a member of the class consisting ofnitrile radicals, and amide and thioamide radicals having at least onehydrogen atom attached nitrogen. a 12. A resinous composition comprisingthe product of reaction of methylene cyanide and formaldehyde. I

13. A resinous composition comprising the product of reaction ofcyanoacetamide and formaldehyde.

14. A resinous composition comprising the product of reaction of amixture comprising formaldehyde, malonic diamide and a phenol.

15. A light-colored resinous composition comprising the product ofreaction of phenol-aldehyde condensation product and the product ofreaction of a mixture comprising an aliphatic aldehyde and at least oneorganic compound having the graphic structure r x where X is a member ofthe class consisting of nitrile radicals, and amide and thioamideradicals havingat least one hydrogen atom attached directly to the amidenitrogen.

.16. A heat-convertible resinous composition comprising a soluble,fusible resinous reaction product of a mixture comprising formaldehydeand at least one organic compound having the graphic structure I where Xis a member of the class consisting. of nitrile radicals, and amide andthioamide radicals having at least one hydrogen atom attached directlyto the amide nitrogen.

1'7. A product comprising the cured resinous composition of claim 16.

18. A light-colored molded article comprising a cellulosic filler and aninsoluble, infusible resinous condensation product of malonic diamide,

- phenol and formaldehyde.

19. A light-colored molded article produced by molding under heat andpressure a composition comprising the product of reaction ofphenolaldehyde condensation product and the product of reaction of amixture comprising an aliphatic aldehyde and at least one organiccompound having the graphic structure X CH2 where X is a member of theclass consisting of nitrile radicals, and amide and thioamide radicalshaving at least one hydrogen atom attached directly to the amidenitrogen.

20, The method of producing a resinous composition especially adaptedfor use as a molding composition, a casting resin or a varnish, saidmethod comprising reacting to resin formation a mixture comprising analiphatic aldehyde and at least one organic compound having the graphicstructure Y x where X is a member of the class consisting of nitrileradicals, and amide and thioamide radicals having at least one hydrogenatom attached directly to the amide nitrogen.

GAETANO F. DALELIO.

